Metal halide-ester reaction process and compositions

ABSTRACT

New compositions useful as antiperspirants are derived from the reaction of a metal halide Lewis acid with at least one ester selected from pyrocarbonates, carbonates and ortho formates, with or without subsequent further reaction with an organic hydroxylcontaining compound.

Enited Mates Etent Eein et all.

H lMiarch 20, T973 METAL HALIIIDE ESTER REACTII'ON PRUCESS AND CUMEUSTTTUNS Inventors: Marvin Michael Eein, Westfield;

,Tohn James Roderick, Paramus. both ofNJ.

Assignee: Dart Industries, llnc., Los Angeles,

Calif.

Filed: May 28, 1971 Appl. No.: 148,122

US. Ci. ..260/448 R, 106/308 Q, 260/463, 260/615 A, 260/429 R, 260/429.3,

Tint. CT. ..C07li 5/06 Eieid oi Search...260/463, 615 A, 448 R, 439 R, 260/429.5, 429.9, 429.7, 429 R, 429.3

References Cited UNITED STATES PATENTS Unger ..260/463 Ruthruff ....260/463 Anderson et a]. ....260/463 Boudakian ..260/463 3,350,463 10/1967 Hass et a]. ..260/615 A OTHER PUBLICATIONS Primary Examiner-I-Ielen M. B. Sneed Attorney-Fred S. Valles, Richard A. Dannells, Jr. and Margareta LeMaire [5 7] ABSTRACT New compositions useful as antiperspirants are derived from the reaction of a metal halide Lewis acid with at least one ester selected from pyrocarbonates, carbonates and ortho formates, with or without sub sequent further reaction with an organic hydroxylcontaining compound.

13 Claims, No Drawings METAL lllillklLlDllI ESTER REACTTUN PROCESS AND COMPUSITTONS This invention relates to new compositions useful as antiperspirants and as flocculating agents.

Briefly, the invention relates to compositions produced by reaction of a Lewis Acid and an ester coreactant with or without subsequent reaction with an organic hydroxyl-containing compound, all of which are further described hereinafter.

The Lewis acid, for purposes of this invention, is defined as any metal halide electron accepting material relative to the ester co-reactant. Included within this group are the metal halides (chlorides, bromides, iodides and fluorides) of metals and metalloids of the Groups IB and ll through VIII of the Periodic Table. Particularly preferred Lewis acids are the chlorides or bromides of a metal selected from the class consisting of Fe(VIll), Ti (IV), Zn(II), Sn(IV), Al(III), Mo(V), Zr(IV), W(Vll), l-Tf(IV), Nb(V), Ta(V) and B(III). Mixtures of such Lewis acids may also be used.

The ester co-reactants used to produce the compositions of the invention generally include pyrocarbonate esters, carbonate esters and ortho esters. Pyrocarbonate esters are preferred and include those defined by the general formula wherein R, and R independently, are lower alkyl having one to six carbon atoms; aryl, generally phenyl and substituted phenyl wherein the substituents include chlorine and lower alkyl radicals; cycloalkyl, generally cyclohexyl and cyclopentyl; and aralkyl radicals, such as benzyl and phenylethyl wherein the phenyl moiety of the aralkyl substituent may also contain chlorine and lower alkyl substituents. Such pyrocarbonate esters are known in the art and may be prepared by reacting aqueous alkali or alkaline earth metal hydroxide solutions with solutions of chloro-earbonic esters dissolved in water immiscible solvents in the presence of tertiary amines. Preparations of this type are described in US. Pats. No. 3,078,294 and 3,240,796.

While the pyrocarbonate esters may be preferred there may also be used carbonate esters defined by the general formula wherein R and R are the same as R, and R described above with respect to the pyrocarbonate esters. These esters and their preparations are also known in the art.

In addition to the above mentioned esters there may also be employed ortho esters (formates) of the following general formula wherein R R and R are the same as R, and R defined above. These esters and their preparations are also known in the art. Of the ortho esters, the commercially available methyl, ethyl and isodecyl orthoformates are preferred.

The compositions according to this invention are prepared by reacting at least one metal halide Lewis acid with at least one of the ester co-reactants with or without further reaction with an organic hydroxyl-containing compound. The reaction between the metal ha lide and the ester may be conducted in any molar ratio with a hydrocarbon halide being split off and generally evolved as a gas. However, in a preferred form of the invention wherein the intended use of the composition is as an antiperspirant, it is desirable to react a stoichiometric equivalent or excess of the ester in proportion to the metal halide in order to replace as much of the halide as possible. Halides are irritants to the skin and therefore by using at least a stoichiometric amount of the ester it is thereby assured that, theoretically, sufficient ester is present to completely react with the metal halide and yield a less irritating composition.

The reaction is conducted in an inert medium, that is, a diluent which can include any aprotic diluent for the Lewis-acid. Preferred members of such class are lower alkyl chlorides such as carbontetrachloride, methylene chloride and chloroform. These diluents for the Lewis acids are also generally found to function as solvents for the product. When a pyrocarbonate or orthoformate is used, it is generally required to use anyhydrous conditions in view of the irreversible hydrolysis which occurs in the presence of water.

The reaction ingredients can be mixed in any sequence. However the preferred technique is to disperse the metal halide in the diluent and then slowly add the ester. The reverse form of addition, that is, the addition of the ester to the diluent, and subsequent addition of the metal halides is possible but generally results in a slower reaction (presumably due to the fact that the metal halide, as it drops into the reaction flask, is initially coated and therefore the reaction rate is reduced).

The reaction proceeds spontaneously and is exothermic in nature. If necessary, cooling should be applied to avoid such high temperatures as would result in decomposition. Generally, the temperature during reaction should be maintained in a range from O-200C with the preferred temperature range being 2060C. The reaction mixture should be stirred due to the formation of a heavy precipitate during reaction. During reaction the precipitate which initially forms is gradually redissolved and the ultimate reaction mixture is gradually redissolved and the ultimate reaction mixture is rather viscous and syrupy. Also during reaction, gaseous hydrocarbon halide is generally evolved at a very rapid rate even at room temperature. Therefore it is advisable to slowly add the ester to the reaction medium. The reaction is completed when the exothermic heat ceases and generally corresponds to cessation of the evolution of hydrocarbon halide or after the elapse of a short period of time following completion of the addition of the reactants. It is desirable to heat and stir the reaction mixture for a period of time after evolution of the gas in order to insure substantial removal of any entrapped gases.

At the end of the reaction a dry, free-flowing powder may be produced by removal of volatile material such as the diluent and excess reactants according to conventional techniques. For example, recovery may be by distillation at a temperature below the decomposition point of the resulting metal-containing reaction product or vacuum stripping at lower temperatures until the composition results in the form of a powder. This composition can also be recovered by crystallization from the diluent by cooling at e.g. -C for several hours and filtering or by such crystallization after first removing the major portion of diluent by evaporation.

While the recovery of these compositions is within the skill of the art, it should be pointed out that in the case of aryl esters as reactants an aryl halide will result which will not be extremely volatile and in some cases will also be soluble in the reaction medium. These situations will require more effort in recovery of the product but still involve no more than conventional techniques.

The compositions prepared as described above are useful as antiperspirants and may be formulated into such commercial itemsaccording to known techniques and formulations depending upon the form of the commercial item, e.g. roll-on lotions, aerosol sprays, etc. These compositions are also suitable for use as flocculating agents for various colloidal dispersions, such as waste streams from paper mills containing colloidal dispersions of fibrous matter or in sludges containing iron hydroxides.

This invention not only includes the above compositions but also includes the reaction products resulting from further reacting the above compositions with a non-hindered organic hydroxyl-containing material such as C to C, alkanol or C C. cycloalkanol or phenol, preferably with a C -C alkanol, more preferably with a C -C alkanol. This reaction will generally require addition of some heat for a period of time to insure completion of the reaction. A very convenient manner in which to arrive at these further reaction products is to apply a conventional recrystalliza tion technique using an alkanol to the composition produced by reacting the metal halide with the ester. The recrystallization product will be the reaction product which also functions as an antiperspirant and flocculent.

While the precise structures of the compositions of this invention have not been identified with any certainty they have been ascertained, as will be apparent from the examples hereinafter, to include both of the above mentioned groups of derivatives, namely (1) the solid reaction product of the metal halide and ester as hereinbefore defined and (2) the further reaction product of (l) with a non-hindered organic hydroxylcontaining material. Both groups of derivatives are particularly useful as antiperspirants for dispensing in the form of a spray (dispersed in fluorocarbons such as Freons), a rub-on stick (dispersed in waxes), a roll-on (suspended in a cream), etc.

The invention is further illustrated by reference to the following examples showing preferred forms thereof.

EXAMPLE I Part A. A 2,000 milliliter, 3-necked flask was fitted with a water-cooled reflux condenser which in turn was connected to a trap; a thermometer and dropping funnel were also fitted to the reaction flask as well as a mechanical stirrer.

To the flask was charged 300 cc chloroform and 67 grams Al Cl, (0.5 mole) and the mixture was stirred.-

during reaction in order to break up the white solid precipitate which gradually redissolved. The reaction mixture after about 2 hours was a brown viscous product. After evolution of gas had ceased during reaction, the mixture was heated to 60C and held for about 30 minutes to further de-gas the mixture. Chloroform and ethyl chloride were removed with moderate vacuum and the excess diethylpyrocarbonate was removed with 2-20 millimeters vacuum at 45-50C. The reaction product was recovered as a powder of varying color, generally brownish, in a yield of about 78 grams.

Part B. The above procedure was repeated but the reaction product was recovered by crystallization. In this process the reaction mixture was chilled to about 5C for 1 hour whereupon crystals formed and were filtered off and washed with CCl,. The major portion of the diluent was removed by vacuum distillation at 45-50C and the remaining mixture cooled to -5C with resulting crystals also recovered. Part C. The reaction products from (A) and (B) were purified by slurrying with 500 cc Ligroine for 10 minutes at 4S-50C, filtering, and washing with cold Ligroine. There was no color change but the melting point range increased by about 10C from about 6370C to 7378C. The elemental analyses on the reaction products produced evidenced a content as follows: aluminum 13.08 percent, carbon 17.42 percent, hydrogen 5.28 percent, chlorine (ionic) 29.12 percent, chlorine (total) 29.23 percent, molecular weight of the product 126 or multiples thereof.

EXAMPLE II The procedure of Example I was repeated using a mole ratio of 2 moles diethylpyrocarbonate per mole aluminum chloride. In this example 162 grams diethylpyrocarbonate (1.0 mole) was added over a period of 1 hour. The temperature again initially rose from room temperature to about 47C and then began to decrease, whereupon heat was added to return the reaction medium to 45C.

At the end of the reaction the chloroform was distilled off and the product was recovered by vacuum distillation to dryness to yield 103 grams of an amorphous reaction product conforming to the elepyrocarbonate (per mole aluminum chloride), 3 mental analysis in Example 1. moles of dibutyl carbonate, diphenyl carbonate, dicyclohexyl carbonate, dibenzyl carbonate, EXAMPLEIH propyl-phenyl-carbonate, ethyl-cyclohexyl car- The procedure of Example ll was repeated at mole bonatei. l y 'p y y ration 2:1 and the product was chilled for one and respondmg reaction P F to those Obtamed a half hours following cessation of gas production, Examples I and IV are obtamed' the product was then filtered to yield approximate EXAMPLE V ly 81 grams concentrate and refrigerated overnight until crystals were again visible in the filtrate. The When the p of Example I Y are reaction product which was produced had a meltreproduced Instead of moles f y ing point of approximately 69C and conformed to pymcarbonalt'e (Per mole alummum chlofldex 3 the elementalanalysisin pxamplep moles of (tri) methyl ortho formate; (trl) ethyl l5 orthoformate; (trl)1sodecyl orthoformate; EXAMPLE lV (tri)phenyl ortho formate; (tri)cyclohexyl ortho formate; (tri)benzyl ortho formate; (di)propyl, phenyl ortho formate; ethyl (di)cyclohexyl orthoformate; or (di)ethyl, phenylethyl orthoformate, corresponding reaction products similar to those obtained in Examples I and IV are obtained.

The procedure of Example I was followed using 201 grams aluminum chloride (1.5 moles), 575 cc. chloroform and 730 grams (4.5 moles) diethylpyrocarbonate. The ester was added dropwise over a period of 2 hours. About 270 grams of a solid reaction product melting at about 78-84C were EXAMPLE Vlll recovered by crystallization procedures as outlined in Example I B. About 50 grams of the reaction product were dissolved in 500 cc of ethyl alcohol (absolute) heated to 4550C. 5 grams of Darco S-Sl was added and the mixture was held at reaction products are obtained corresponding to f0]? 10 minutes While Stirling The Slurry the respective metal of the metal halide employed. was filtered through a filter aid y AW) Although the compositions of this invention in their When Examples V, VI, and Vll are reproduced using 25 instead of 1 mole Al C1 1 mole of Fe C1 SnCl ZnCI M0Cl ZrCl WCI HfCl TaCl NvCl BCl or the bromide, iodide, or fluoride, similar and the alcohol removed y Vacuum pp g to use as antiperspirants can be applied in any composidrynasi The final reaction Product recovered tion having an aqueous and/or alcoholic base, it is yiel ed 475 grams, a elemental n ly preferred to use the final derivative obtained upon showed an aluminum content 13.35 percent, reaction with the hydroxyl-containing compound when carbon content 5.99 percent, hydrogen content an alcoholic base is utilized since the other derivatives 5.26 percent and chlorine (ionic and total) will react with the alcohol and may present packaging 18.98 percent. IR curves run on this final reaction problems. However, this is not essential since both product differed radically from the lift curves obd rivativ s functi n as anti-perspirants.

mi d f h action product mcovered i E in formulating antiperspirants it is possible to use ample I b vacuum di ill i or lli i 40 roll-on lotions, pou'rable compositions, creams, imand not subject to contact with ethyl alcohol. This Pregnated Pads, Sticks, aerosol p y of p fi h theory that a derivative is f d by Suitable formulations are known to the art, however reaction with the hydroxyl group in the Organic some typical formulations will be set forth below.

hydroxyl group-containing compound (ethyl al- TABLE I cohol). The same type of derivative will be formed with other alltanols such as isopropanol, methanol, C T H Pans fag S omposl IO 0 IS ll'lVCnIlOfl butanol and hexanol' Composition of this invention 10-50 The elemental analyses performed in this example Water k 5-30 Anti-tac agent (for example, and in Example I were conducted according to water Somme fluid silicone methods of the Schwarzkopf Mlcroanalytical Lab. polymers h as w Corning Silicone (SH-004) 0-5 EXAMPLE V Anhydrous ethanol 0-60 Film-forming resin for inhibiting ,3 transfer of the composition When the procedures of Example l or IV are andreducingsminingflm reproduced using instead of 3 moles d1ethyl55 example,copolymerof lauryl methacrylate-NNdiethyl pyrocarbonate (per mole aluminum chloride), 3 ethylolaminoethylmethacrylaw' moles of dibutyl pyrocarbonate, diphenyl pyrocarquaternized disulfate 0-4 bonate, dicyclohexyl pyrocarbonate, dibenzyl Perfume and pyrocarbonate, propyl-phenyl-pyrocarbonate,

ethyl cyclohexyl pyrocarbonate or ethybphenyl When the antiperspirant is to be used in an aerosol ethyl-pyrocarbonate, corresponding reaction bomb a typlcal formulano as follows:

products similar to those obtained in Examples l TABLE and IV are obtained.

Parts by Weight EXAMPLE VI 5 Composition of this invention 4-15 Anhydrous ethanol 20-60 When the procedure of Examples l or IV are (mmnal use of invention) reproduced using instead of 3 moles diethyl Emollient(forexample,solubleesters alcohol and other components giving good skin touch such as oleyl alcohol, triethyl citrate, propylene glycol monolaurate, diethyl phthalate, lanolin stearol fraction Perfum solubilizer (for example,

alcohol soluble surfactive agents such as ethoxylated nonyl phenol, etc.)

Anti-tack agents (for example,

methyl phenyl polysiloxane Dow Corning 550) Perfume Liquified propellant (fluorinated or fluorochlorinated lower saturated aliphatic hydrocarbons-Freons) TABLE III Parts by Weight Composition of this invention l0-25 Propylene glycol l-4 Polyoxyethylene monostearate 95-4 Methyl cellulose 0-l .5 Water 65-80 Perfume 0.5

Multiple active ingredients can be utilized in the noted compositions.

The perfumes typically used in all of the noted compositions are, for example, sweet floral-aldehydic types as well as various floral odors and spice-type odors (for example, lavendar, lime or lemon odors).

Both the ester-Lewis acid reaction product and the alcoholic reaction product thereof have been tested on rabbits according to the 20 day subacute dermal toxicity study conducted by the methods of Carter Products Inc. After a dosage of 180 mg./kg. of the ester-Lewis acid reaction product applied separately each day over percent of the body, which had been shaved, no deaths or abnormal patterns were noticed after days and no irritation resulted. The same good results were achieved with 180 mg./kg of the alcoholic reaction product thereof directly applied by this method.

Thus, having described the invention in detail it will be understood by those skilled in the art that certain variations and modifications may be made without departing from the spirit and scope of the invention as described herein or in the appended claims.

We claim:

1. A process for producing a metal-containing reaction product comprising reacting at least one metal halide Lewis acid with at least one ester of the group defined by the following formulas:

wherein each of R R R and R are, independently selected from alkyl, aryl, cycloalkyl, or aralkyl radicals, said reaction being conducted in an aprotic diluent at temperatures below the decomposition point of the reactants and the metal-containing reaction product.

2. A process according to claim 1 wherein the reaction is conducted at a temperature in the range of 0 to 200C.

3. A process according to claim 1 wherein the ester is present at least in a stoichiornetric amount.

4. A process according to claim 1 wherein the ester is defined by the formula of (I) and the reaction is conducted under anhydrous conditions.

5. A process according to claim 1 wherein the metal containing reaction product is further reacted with an organic hydroxy-containing compound selected from a C -C, alkanol, C -C cycloalkanol or phenol.

6. A metal-containing reaction product derived by reacting at least one metal halide Lewis acid with at least one ester of the group defined by the following formulas:

wherein each of R R R and R are independently, selected from alkyl, aryl, cycloalkyl, or aralkyl radicals. 7. A metal-containing reaction product according to I claim 6 wherein the alkyl radical has one to six carbon atoms, the aryl radical is phenyl or phenyl substituted with chlorine or C -C alkyl radicals, the cycloalkyl radical is cyclohexyl or cyclopentyl, and the aralkyl radical is benzyl or phenylethyl wherein the phenyl moieties are unsubstituted or substituted with chlorine or C,-C, alkyl radicals.

8. A metal-containing reaction product according to claim 6 wherein the metal of the metal halide Lewis acid is selected from the metals and metalloids of Groups IB and II through VIII of the Periodic Table.

9. A metal-containing reaction product according to claim 6 wherein the reaction product of the metal halide Lewis acid and ester is further reacted with an organic hydroxyl-containing compound selected from a C,-C, alkanol, C -C cycloalkanol, or phenol.

10. A metal-containing reaction product derived by reacting aluminum chloride with a dialkyl pyrocarbonate wherein the alkyl radicals have one to six carbon atoms.

11. A metal-containing reaction product according to claim 10 wherein the reaction product of the aluminum chloride and dialkyl pyrocarbonate is further reacted with an alkanol having one to seven carbon atoms.

12. A process for producing a metal-containing reaction product comprising reacting at least one ester of the group defined by the following formulas:

13. A metal-containing reaction product derived by reacting at least one ester of the group defined by the following formulas:

(n R; o-o-oR.

6 wherein each of R R R and R are, independently,

selected from alkyl, aryl, cycloalkyl, or aralkyl radicals with at least one metal halide Lewis acid selected from chlorides or bromides of Fe, Ti, Zn, Sn, Al, Mo, Zr, W, Hf, Nb, Ta, or B. 

2. A process according to claim 1 wherein the reaction is conducted at a temperature in the range of 0* to 200* C.
 3. A process according to claim 1 wherein the ester is present at least in a stoichiometric amount.
 4. A process according to claim 1 wherein the ester is defined by the formula of (I) and the reaction is conducted under anhydrous conditions.
 5. A process according to claim 1 wherein the metal containing reaction product is further reacted with an organic hydroxy-containing compound selected from a C1-C12 aLkanol, C4-C8 cycloalkanol or phenol.
 6. A metal-containing reaction product derived by reacting at least one metal halide Lewis acid with at least one ester of the group defined by the following formulas:
 7. A metal-containing reaction product according to claim 6 wherein the alkyl radical has one to six carbon atoms, the aryl radical is phenyl or phenyl substituted with chlorine or C1-C6 alkyl radicals, the cycloalkyl radical is cyclohexyl or cyclopentyl, and the aralkyl radical is benzyl or phenylethyl wherein the phenyl moieties are unsubstituted or substituted with chlorine or C1-C6 alkyl radicals.
 8. A metal-containing reaction product according to claim 6 wherein the metal of the metal halide Lewis acid is selected from the metals and metalloids of Groups IB and II through VIII of the Periodic Table.
 9. A metal-containing reaction product according to claim 6 wherein the reaction product of the metal halide Lewis acid and ester is further reacted with an organic hydroxyl-containing compound selected from a C1-C12 alkanol, C4-C8 cycloalkanol, or phenol.
 10. A metal-containing reaction product derived by reacting aluminum chloride with a dialkyl pyrocarbonate wherein the alkyl radicals have one to six carbon atoms.
 11. A metal-containing reaction product according to claim 10 wherein the reaction product of the aluminum chloride and dialkyl pyrocarbonate is further reacted with an alkanol having one to seven carbon atoms.
 12. A process for producing a metal-containing reaction product comprising reacting at least one ester of the group defined by the following formulas: wherein each of R1, R2, R3 and R4 are, independently, selected from alkyl, aryl, cycloalkyl, or aralkyl radicals, with at least one metal halide Lewis acid selected from chlorides or bromides of Fe, Ti, Zn, Sn, Al, Mo, Zr, W, Hf, Nb, Ta, or B, said reaction being conducted in an aprotic diluent at temperatures below the decomposition point of the reactants and the metal-containing reaction product.
 13. A metal-containing reaction product derived by reacting at least one ester of the group defined by the following formulas: wherein each of R1, R2, R3 and R4 are, independently, selected from alkyl, aryl, cycloalkyl, or aralkyl radicals with at least one metal halide Lewis acid selected from chlorides or bromides of Fe, Ti, Zn, Sn, Al, Mo, Zr, W, Hf, Nb, Ta, or B. 